Compositions containing a liquid medium and an azo dye

ABSTRACT

A composition comprising: 
     (a) a liquid medium comprising (i), (ii) or (iii): 
     (i) a mixture of water and an organic solvent; 
     (ii) an organic solvent free from water; or 
     (iii) a low melting point solid; and 
     (b) a dye of the Formula (1) or a salt thereof:                    
      wherein A, B, Z, L, R 1  and n are as defined in the description. Also claimed are certain dyes of Formula (1), inks, an ink jet printing process using the inks, a substrate printed with the inks, an ink jet printer cartridge containing the inks and an ink jet printer containing the ink jet printer cartridge.

This application is the national phase of international applicationPCT/GB99/03025 filed Sep. 13, 1999 which designated the U.S.

This invention relates to compositions, to inks and to dyes and to theiruse in ink jet printing (“IJP”). IJP is a non-impact printing techniquein which droplets of ink are ejected through a fine nozzle onto asubstrate without bringing the nozzle into contact with the substrate.

There are many demanding performance requirements for dyes and inks usedin IJP. For example they desirably provide sharp, non-feathered imageshaving good water-fastness, light-fastness and optical density. The inksare often required to dry quickly when applied to a substrate to preventsmudging, but they should not form a crust over the tip of an ink jetnozzle because this will stop the printer from working. The inks shouldalso be stable to storage over time without decomposing or forming aprecipitate which could block the fine nozzle.

According to a first aspect of the present invention there is provided acomposition comprising:

(a) a liquid medium comprising (i), (ii) or (iii):

(i) a mixture of water and an organic solvent;

(ii) an organic solvent free from water; or

(iii) a low melting point solid; and

(b) a dye of the Formula (1) or salt thereof:

 wherein:

each A independently is N, C—Cl, C—CN or C—NO₂;

each B independently is a substituent other than —COOH;

L is optionally interrupted alkylene, optionally substituted by halo or—OH, wherein the optional interruption(s) are selected from —O—, —S—,—NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—;

each Z independently is —SR², —OR³, —NR⁴R⁵ or a labile atom or group;

each X independently is —S—, —O— or —NR¹—;

each R¹ independently is H or optionally substituted alkyl;

R², R³, R⁴ and R⁵are each independently H, optionally substituted alkyl,optionally substituted aryl or optionally substituted aralkyl; or

R⁴ and R⁵ together with the nitrogen to which they are attached form anoptionally substituted five or six membered ring; and

each n independently is 0 to 4.

Preferably the dye of Formula (1) is not of the Formula (A), (B), (C) or(D):

wherein X¹ is H or Na;

Preferably the composition has a concentration of less than 100 partsper million in total of halide ions and divalent and trivalent metalions.

Preferably the group —XLX— shown in Formula (1) is not of the Formula(E), (F), (G), (H), (I) or (J):

—HN—V—O(—G—O—)_(p)W—NH—  Formula (E)

wherein: V and W each independently represents a linear or branchedalkylene group having from 1 to 8 carbon atoms; G represents a linear orbranched alkylene group having from 1 to 2 carbon atoms or the followingformula (a):

and p represents a number of from 0 to 20;

wherein G¹ and G² each represents a hydrogen atom or a methyl group;

Preferably each A is N.

Preferably each R¹ independently is H or optionally substitutedC₁₋₆alkyl, more preferably H or C₁₋₄-alkyl optionally substituted by—OH, —COOH, —SO₃H or —CN. It is especially preferred that each R¹independently is methyl, ethyl or H, more especially H.

Each X independently is preferably —S— or —NR¹—, more preferably —NR¹—and especially —NH—.

Each B independently is preferably —SO₃H, —PO₃H₂,—CF₃, optionallysubstituted alkoxy, optionally substituted alkyl, optionally substitutedamino, halo, —CN, —SO₂—T, —OH or —NO₂, wherein T is optionallysubstituted alkyl, optionally substituted aryl, vinyl, or a groupconvertible to vinyl on treatment with aqueous alkali. When T is a groupwhich is convertible to vinyl on treatment with aqueous alkali it ispreferably of the formula —CH₂CH₂OSO₃H, —CH₂CH₂SSO₃H, —CH₂CH₂Cl or—CH₂CH₂OCOCH₃. More preferably T is —CH═CH₂ or —CH₂CH₂OSO₃H andespecially —CH═CH₂.

More preferably each B independently is —SO₃H, —PO₃H₂, —CF₃, optionallysubstituted C₁₋₁₀-alkoxy, optionally substituted C₁₋₁₀-alkyl, optionallysubstituted amino, —SO₂CH═CH₂, —F, —Cl, —CN, —OH or —NO₂. When B issubstituted the substituent(s) is/are preferably selected fromC₁₋₆-alkyl, C₁₋₆-hydroxyalkyl, C₁₋₆-alkoxy, C₁₋₄-alkylCO, —OH, —SO₃H,—COOH, —CN, —PO₃H₂, halo and —NH₂.

Still more preferably each B independently is —SO₃H, —CF₃, amino,—NHCOC₁₋₄-alkyl, C₁₋₆-alkoxy or C₁₋₆-alkyl optionally substituted by—OH, —COOH, —NH₂ or —SO₃H. It is especially preferred that each Bindependently is C₁₋₄-alkyl or —NHCOC₁₋₄-alkyl, more especially methyl,ethyl or —NHCOCH₃.

Preferably each n independently is 0, 1 or 2, more preferably 0.

When R², R³, R⁴, R₅ or T is optionally substituted alkyl it ispreferably optionally substituted C₁₋₂₀-alkyl, more preferablyoptionally substituted C₁₋₁₀-alkyl and especially optionally substitutedC₁₋₆-alkyl. Preferred optional substituents include C₁₋₆-alkoxy,C₁₋₆-hydroxyalkoxy, —OH, —COOH, —SO₃H, —PO₃H₂, —CN, a 5 or 6 memberedheterocyclic group and optionally substituted amino. Preferred 5 or 6membered heterocyclic groups are optionally substituted furanyl,tetrahydrofuranyl, piperazinyl and niorpholinyl.

When any of R², R³, R⁴, R⁵ or T is optionally substituted aryl it ispreferably optionally substituted phenyl or naphthyl, more preferablyoptionally substituted phenyl. Preferred optional substituents areC₁₋₆-alkoxy, halo (preferably F or Cl), —OH, —CN, —COOH, —SO₃H, —PO₃H₂,—NO₂, —NH₂, —COC₁₋₄-alkyl, —NHCOC₁₋₄-alkyl,—(C₁₋₆-alkylene)O(C₁₋₆-alkylene)OC₁₋₄-alkyl,—(C₂₋₆-alkylene)O(C₂₋₆-alkylene)OH, C₁₋₆-alkyl, —SO₂NH₂,—SO₂NHC₁₋₄-alkyl or C₁₋₆-alkyl substituted by —OH, —COOH or —SO₃H.

When any of R², R³, R⁴ or R⁵ is optionally substituted aralkyl it ispreferably of the formula:

each R⁵ independently is C₁₋₄-alkyl, C₁₋₄-alkoxy, halo, —OH, —NH₂,—COOH, —SO₃H or —PO₃H₂; and

a is 0 to 5.

a is preferably 0, 1 or 2, more preferably 0 or 1.

When R⁴ and R⁵ together with the nitrogen to which they are attachedform an optionally substituted 5 or 6 membered ring it is preferably anoptionally substituted piperazine, piperidine or morpholine ring. Thesubstituents are preferably selected from —OH, —COOH, —SO₃H,C₁₋₆-alkoxy, C₁₋₆-alkyl and C₁₋₆-alkyl substituted by —OH, —COOH or—SO₃H.

When Z is a labile atom or group, it is preferably an atom or groupwhich is displaceable by a hydroxyl group of cellulose under mildlyalkaline aqueous conditions to form a covalent bond between the dye ofFormula (1) and cellulose.

Preferred labile atoms and groups which may be represented by Z includehalogen atoms, for example F or Cl; sulphonic acid groups; thiocyanogroups; quaternary ammonium groups, for example trialkylammonium groupsand optionally substituted pyridinium groups, for example 3- and4-carboxy pyridinium groups. An especially preferred labile atom is Cl.

It is preferred however that each Z independently is —SR², —OR³ or—NR⁴R⁵, more preferably —OH, —SR² or —NR⁴R⁵ wherein R², R⁴ and R⁵ are ashereinbefore defined. It is especially preferred that each Zindependently is —NR⁷R⁸ wherein R⁷ is C₁₋₆-alkyl optionally substitutedby —OH, C₁₋₄-alkoxy, C₁₋₄-hydroxyalkoxy, —COOH or —SO₃H; and R⁸independently is as defined for R⁷or H.

For ease of synthesis it is preferred that each Z is the same in Formula(1).

L is preferably a branched, monocyclic (for example cyclohexylene) ormore preferably linear alkylene group. Preferably L is optionallyinterrupted C₁₋₂₀-alkylene, wherein the optional interruptions are ashereinbefore defined. More preferably L is C₂₋₂₀-alkylene optionallyinterrupted by —O—, —S—, —CH═CH— or —NR¹— wherein R¹ is as hereinbeforedefined. It is especially preferred that L is C₂₋₆-alkylene, moreespecially ethylene (i.e. —CH₂CH₂—).

When L is interrupted it preferably contains a single interrupting groupor two or more interrupting groups, for example an —SS— group. Preferredinterrupting groups are selected from one or more of —S—, —CH═CH— and—NR¹— wherein R¹ is as hereinbefore defined.

Examples of optionally substituted alkylene groups represented by Linclude: ethylene; 1,2- & 1,3-propylene; 2-hydroxy-1,3-propylene 1,4-,2,3- and 2,4-butylene; 2-methyl-1,3-propylene; 2-methyl-2,4-pentylene;2,2-dimethyl-1,3-propylene; 1-chloro-2,3-propylene; 1,6- and1,5-hexylene; 2,7-heptylene; 3-methyl-1,6-hexylene and1,4-cyclohexylene. Examples of interrupted alkylene groups representedby L include: —CH₂NHCH₂—; —CH₂CH═CHCH₂—; —CH₂CH₂OCH₂CH₂—;—CH₂CH₂SSCH₂CH₂— and —CH₂CH₂SCH₂CH₂—.

The floating sulpho groups in Formula (1) are preferably attached metato the —NR¹— group.

In a first preferred embodiment of the present invention, when bothgroups represented by X in Formula (1) are NH, then L is cyclohexyleneor optionally interrupted linear or branched chain alkylene, optionallysubstituted by halo or —OH, wherein the optional interruption(s) areselected from —S—, —NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—, wherein R¹ isas hereinbefore defined.

In a second preferred embodiment L in Formula (1) is optionallyinterrupted linear or branched alkylene, optionally substituted by haloor —OH, wherein the optional interruption(s) are selected from —S—,—NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—, wherein R¹ is as hereinbeforedefined.

In the first and second preferred embodiments L is preferably a linearC₂₋₂₀-alkylene group optionally interrupted by —S—, —CH═CH— or —NR¹—wherein R¹ is as hereinbefore defined. It is especially preferred that Lis C₂₋₆-alkylene.

In view of the foregoing preferences, the dye of the Formula (1) used inthe compositions of the present invention is preferably of Formula (2)or a salt thereof:

wherein:

L¹ is optionally interrupted C₂₋₂₀-alkylene, wherein the optionallyinterruption(s) are selected from —O—, —S—, —CR⁹═CR⁹— or —NR⁹—;

each R⁹ independently is H or C₁₋₄-alkyl optionally substituted by —OH,—COOH, —SO₃H or —CN; and

each Z independently is as hereinbefore defined.

Preferred dyes of the Formula (2) used in the composition are not of theFormula (A), (B), (C) or (D) as hereinbefore defined.

Preferably L¹ is optionally interrupted linear or branchedC₂₋₂₀-alkylene, wherein the optional interruption(s) are selected from—S—, —CR⁹═CR⁹— or —NR⁹— wherein R⁹ is as hereinbefore defined. Morepreferably L¹ is a linear C₂₋₂₀-alkylene group. It is especiallypreferred that L¹ is C₂₋₆-alkylene.

Each R⁹ preferably independently is H or C₁₋₄-alkyl optionallysubstituted by —OH, more preferably H.

More preferably in the dyes of Formula (2) the group —NR⁹L¹NR⁹— is notof the Formula (E), (F), (G), (H), (I) or (J) as hereinbefore defined.

Especially preferred dyes of the Formula (2) are those in which L¹ isC₂₋₄-alkylene and each Z independently is —NR⁷R⁸ wherein R⁷ and R⁸ areas hereinbefore defined; more especially those in which L¹ isC₂₋₄-alkylene, each Z independently is —NR⁷R⁸ and each R⁹ is H.

The dyes of Formula (1) may be in the free acid or salt form. Preferredsalts are water-soluble, for example alkali metal salts, especiallylithium, sodium and potassium salts, ammonium and substituted ammoniumsalts. Especially preferred salts are salts with sodium, lithium,ammonia, volatile amines and mixed salts thereof, especially mixedlithium/sodium salts. The dyes may be converted into a salt using knowntechniques. For example, an alkali metal salt may be converted into asalt with ammonia or an amine by dissolving an alkali metal salt inwater, acidifying with a mineral acid and adjusting the pH of thesolution to pH 9 to 9.5 with ammonia or the amine and removing thealkali metal cations by dialysis, reverse osmosis or ultrafiltration.

Component (b) of the composition according to the first aspect of theinvention may comprise a single dye of Formula (1) or two or more dyesof the Formula (1) as hereinbefore defined.

The composition may also further contain one or more magenta dyes otherthan a dye of Formula (1). Accordingly, the composition preferablycomprises:

(a) from 99.99 to 70, more preferably from 99.9 to 80, especially from99.5 to 85, and more especially from 99 to 95 parts in total of theliquid medium;

(b) from 0.01 to 30, more preferably 0.1 to 20, especially from 0.5 to15, and more especially from 1 to 5 parts of one or more dyes of theFormula (1) or salt thereof; and

(c) from 0 to 30, more preferably from 0 to 20, especially from 0.01 to15 parts of a magenta dye other than a dye of Formula (1) or saltthereof;

wherein all parts are by weight and the sum of the parts(a)+(b)+(c)=100.

The liquid medium preferably comprises water or, more preferably, (i),(ii) or (iii), especially when Z is a labile atom or group:

(i) a mixture of water and an organic solvent;

(ii) an organic solvent free from water; or

(iii) a low melting point solid.

When the liquid medium is a mixture of water and an organic solvent, oran organic solvent free from water; the dye is preferably completelydissolved in the medium.

Preferably the dye has a solubility in the medium at 20° C. of at least10%. This allows the preparation of concentrates which may be used toprepare more dilute inks and reduces the chance of the dye(s)precipitating if evaporation of the liquid medium occurs during storage.

When the liquid medium comprises a mixture of water and an organicsolvent, the weight ratio of water to organic solvent is preferably from99:1 to 1:99, more preferably from 99:1 to 50:50 and especially from95:5 to 80:20.

It is preferred that the organic solvent present in the mixture of waterand organic solvent is a water-miscible organic solvent or a mixture ofsuch solvents. Preferred water-miscible organic solvents includeC₁₋₆-alkanols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol andcyclohexanol; linear amides, preferably dimethylformamide ordimethylacetamide; ketones and ketone-alcohols, preferably acetone,methyl ether ketone, cyclohexanone and diacetone alcohol; water-miscibleethers, preferably tetrahydrofuran and dioxane; diols, preferably diolshaving from 2 to 12 carbon atoms, for example pentane-1,5-diol, ethyleneglycol, propylene glycol, butylene glycol, pentylene glycol, hexyleneglycol and thiodiglycol and oligo- and poly-alkyleneglycols, preferablydiethylene glycol, triethylene glycol, polyethylene glycol andpolypropylene glycol; triols, preferably glycerol and 1,2,6-hexanetriol;mono-C₁₋₄-alkyl ethers of diols, preferably mono-C₁₋₄-alkyl ethers ofdiols having 2 to 12 carbon atoms, especially 2-methoxyethanol,2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol,2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol and ethyleneglycol monoallylether;cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclicesters, preferably caprolactone; sulphoxides, preferably dimethylsulphoxide and sulpholane. Preferably the liquid medium comprises waterand 2 or more, especially from 2 to 8, water-miscible organic solvents.

Examples of further suitable liquid media comprising a mixture of waterand one or more organic solvents are described in U.S. Pat. No.4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284, EP 425,150Aand U.S. Pat. No. 5,207,824.

When the liquid medium comprises an organic solvent free from water,(i.e. less than 1% water by weight) the solvent preferably has a boilingpoint of from 30° to 200° C., more preferably of from 40° to 150° C.,especially from 50 to 125° C. The organic solvent may bewater-immiscible, water-miscible or a mixture of such solvents.Preferred water-miscible organic solvents are any of the hereinbeforedescribed water-miscible organic solvents and mixtures thereof.Preferred water-immiscible solvents include, for example, aliphatic,hydrocarbons; esters, preferably ethyl acetate; chlorinatedhydrocarbons, preferably CH₂Cl₂; and ethers, preferably diethyl ether;and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent,preferably a polar solvent is included because this enhances solubilityof the dye in the liquid medium. Examples of polar solvents includeC₁₋₄-alcohols. In view of the foregoing preferences it is especiallypreferred that where the liquid medium is an organic solvent free fromwater it comprises a ketone (especially methyl ethyl ketone) &/or analcohol (especially a C₁₋₄-alkanol, such as ethanol or propanol).

The organic solvent free from water may be a single organic solvent or amixture of two or more organic solvents. It is preferred that when themedium is an organic solvent free from water it is a mixture of 2 to 5different organic solvents. This allows a medium to be selected whichgives good control over the drying characteristics and storage stabilityof the composition according to the first aspect of the invention.

Liquid media comprising an organic solvent free from water areparticularly useful where fast drying times are required andparticularly when printing onto hydrophobic and non-absorbentsubstrates, for example plastics, metal and glass.

Preferred low melting point solids have a melting point in the rangefrom 60° C. to 125° C. Suitable low melting point solids include longchain fatty acids or alcohols, preferably those with C₁₈₋₂₄ chains, andsulphonamides. The dye may be dissolved in the low melting point solidor may be finely dispersed in it.

The dyes of Formula (1) exhibit a high solubility in aqueous media,accordingly it is preferred that the liquid medium is a mixture of waterand one or more water-miscible organic solvent(s).

The composition may also contain additional components conventionallyused in ink jet printing inks, for example viscosity and surface tensionmodifiers, corrosion inhibitors, biocides, kogation reducing additives,anti-cockle agents to reduce paper curling and surfactants which may beionic or non-ionic.

The pH of the composition is preferably from 4 to 10.

Component (c) of the composition, when present, is preferably awater-soluble magenta dye, more preferably a xanthene dye, an azo dye ora bis azo dye, especially an anionic azo or bis azo dye and moreespecially an azo or bis azo dye which contains one or more groupsselected from sulphonate, carboxylate and thiocarboxylate groups.

Preferred water-soluble magenta dyes for use as component (c) includeC.I. Acid Red 50, 52, 87, 91, 92, 95, 249 and 289; C.I. Direct Violet106 and 107; compounds 100 to 107, 200 and 201 described on pages 8 and9 of W096/24636; compounds 1 to 24 shown described on cols. 4 to 10 inU.S. Pat. No. 5,542,970; compounds 1 to 55 described on pages 7 to 17 ofEP-A-682 088; compounds 1 to 14 shown in Example 1 to 6 of EP-A-194,885;compounds 1 to 24 described on pages 8 to 13 of EP-A-717 089; thecompounds described in examples 1 to 16 in cols. 5 to 11 of U.S. Pat.No. 5,262,527; the dyes described in Examples 1 to 21 in WO 94/16021;and one or more dyes of the Formula (3) or salts thereof:

wherein:

each V independently is —SO₃H, —COOH, —CF₃, alkoxy, alkyl or —PO₃H₂;

Q is an organic linking group;

each R¹⁰ independently is H or optionally substituted alkyl;

each A independently is N, C—Cl, C—CN or C—NO₂;

each W independently is —SR¹¹, —OR¹², —NR¹³R¹⁴ or halo;

R¹¹, R¹², R¹³ & R¹⁴ are, each independently, H, optionally substitutedalkyl, optionally substituted aryl or optionally substituted aralkyl; or

R¹³ and R¹⁴ together with the nitrogen to which they are attached, forman optionally substituted five or six membered ring;

Especially preferred water-soluble magenta dyes for use as component (c)include C.I. Acid Red 52, C.I. Acid Red 289 and dyes of the Formula (4),(5) and (6):

The dye of Formula (4) may be prepared using the method described inExample 1 of EP-A-559 310. The dye of the Formula (5) may be preparedusing the method described in Example 3 of WO 94/16021. The dye ofFormula (6) may be prepared using to the method described in Example 1of WO 96/24636.

The composition may be used as a concentrate from which inks areprepared, or it may be an ink per se. Preferably the composition is anink, more especially an ink suitable for use in thermal or piezo ink jetprinters.

When the composition according to the first aspect of the invention isused as an ink jet printing ink, the composition preferably has aconcentration of less than 100 parts per million, more preferably lessthan 50 parts per million, in total of halide ions and divalent andtrivalent metals. This reduces nozzle blockage in ink jet printingheads, particularly in thermal ink jet printers. As will be understood,the term “parts per million” refers to parts by weight.

According to a second aspect of the present invention there is provideda dye of the Formula (1) or salt thereof, as hereinbefore defined, withthe provisos:

(i) each Z independently is —SR², —OR³ or —NR⁴R⁵; wherein R², R³, R⁴ andR⁵ are as hereinbefore defined; and

(ii) the dye is not a dye of the Formula (A) wherein X¹ is Na.Preferably the dye is also not of the Formula (A) wherein X¹ is H or ofFormula (B), (C) or (D) as hereinbefore defined.

Preferred dyes of the second aspect of the present invention areselected from the preferred dyes of Formula (1) as hereinbefore definedin relation to the compositions according to the first aspect of thepresent invention. In other words, the preferences described above forthe dyes of Formula (1) used in the compositions also apply to the dyesof the second aspect of the present invention.

Especially preferred dyes of the second aspect of the present inventionare of the Formula (2) and salts thereof as hereinbefore defined, withthe provisos:

(i) each Z independently is —SR², —OR³ or —NR⁴R⁵ wherein R², R³, R⁴ andR⁵ are as hereinbefore defined; and

(ii) the dye of Formula (2) is not a dye of the Formula (A), (B), (C) or(D) as hereinbefore defined.

The dyes of the second aspect of the invention exhibit a high solubilityin aqueous media and provide prints which exhibit high light fastnessand water fastness when incorporated into inks for ink jet printing.

According to a third aspect of the present invention there is provided acomposition comprising:

(i) from 1 to 99 parts, more preferably from 3 to 70 and especially from5 to 50 parts in total of one or more dye(s) of Formula (1) or saltsthereof as hereinbefore defined in the second aspect of the invention;and

(ii) from 99 to 1 parts, more preferably from 30 to 97 parts andespecially 95 to 50 parts in total of one or more water-soluble magentadye(s) other than a dye of the Formula (1) or salt thereof;

wherein all parts are by weight and the sum of the parts (i) and(ii)=100.

Preferred dyes of the Formula (1) in component (i) of the compositionaccording to the third aspect of the invention are selected from thepreferred dyes of Formula (1) described above in the first aspect of theinvention, especially dyes of the Formula (2), and salts thereof.

Preferred water-soluble magenta dyes in component (ii) of thecomposition are selected from the preferred water-soluble magenta dyesdescribed above in relation to component (c) of the compositionaccording to the first aspect of the invention.

The dyes of Formula (1) and Formula (2) may exist in tautomeric formsother than those shown in this specification, for example the hydrazotautomer. These tautomers are included within the scope of the presentclaims. Accordingly the compositions and dyes according to the first,second and third aspects of the invention may comprise tautomers of thedyes of Formula (1) and (2).

The dyes in the composition according to the first aspect of theinvention and the dyes and compositions according to the second andthird aspects of the present invention may be, and preferably are,purified to remove undesirable impurities before they are incorporatedinto inks for ink jet printing. Conventional techniques may be employedfor purifying the dyes, for example ultrafiltration, reverse osmosisand/or dialysis.

The dyes of Formula (1) may be prepared using conventional techniquesfor the preparation of azo dyes. For example a suitable method comprisescondensing a molar excess of the compound of the formula ZH with thecompound of the Formula (7):

wherein L and each Z, B, R¹, X, A and n are as hereinbefore defined.

The condensation is preferably performed in a liquid medium, morepreferably an aqueous medium and especially water. Temperatures of 10°C. to 100° C. are preferred, more preferably from 20 to 95° C.Preferably a reaction time of 1 to 24, more preferably 1 to 4 hours isused.

The condensation is preferably performed in the presence of a suitablebase and optionally with a catalyst, for example4-dimethylaminopynidine.

The base may be any inorganic base for example, ammonia, an alkali metalor alkali earth metal hydroxide, carbonate or bicarbonate, or an organicbase. The amount of base used may be varied between wide limits but itis preferred to use less than 40, more preferably less than 10 andespecially from 3 to 5 moles for each mole of the compound of Formula(7).

After the condensation reaction the product may be isolated byprecipitating the product as a salt from the reaction mixture forexample by the addition of a suitable alkali metal salt, especiallysodium chloride. Alternatively, the product may be isolated in its freeacid form by acidifying the reaction mixture, preferably using a mineralacid, especially hydrochloric acid. Where the product precipitates as asolid it may be separated from the mixture by filtration.

If desired unwanted anions may be removed from the product of the aboveprocess by dialysis, osmosis, ultrafiltration or a combination thereof.

The product of the above process may be converted, if desired, to theNH₄ ⁺, quaternary ammonium or organic amine salt by the addition ofammonia, ammonium hydroxide, primary, secondary, tertiary or quaternaryamine.

The compound of Formula (7) may, for example, be prepared as follows:

stage (a):

diazotising the amine of the Formula (8) and coupling with the compoundof the Formula (9):

 wherein B, n and R¹ are as hereinbefore defined;

stage (b)

hydrolysis, under alkaline conditions, of the acetyl group present inthe product of stage (a);

stage (c)

condensing the product of stage (b) with an approximately molarequivalent of the compound of the Formula (10):

 wherein A is as hereinbefore defined; and

stage (d)

condensing a compound of the formula HX—L—XH with approximately 2 molarequivalents as of the product of stage (c).

The diazotisation in stage (a) is preferably performed in an aqueousmedium at a pH below 7 in the presence of a suitable diazotisationagent. Dilute mineral acid, e.g. HCl or H₂SO₄, is preferably used toachieve the desired acidic conditions. Conveniently-the diazotisationagent is formed in-situ, for example by dissolving an alkali metalnitrite, preferably sodium nitrite, in a molar excess of mineral acid,preferably HCl.

The temperature of the diazotisation is not critical and mayconveniently be carried out at from −5° C. to 20° C., preferably from 0to 10° C. and especially from 0 to 5° C.

The coupling reaction in stage (a) is preferably performed under mildlyalkaline conditions, more preferably at a pH of 7-8.

The hydrolysis in stage (b) is preferably performed in aqueous NaOH at areaction temperature of 50 to 90° C.

The condensations in stages (c) and (d) are preferably performed in thepresence of a base.

A fourth aspect of the present invention provides a process for printingan image on a substrate comprising applying thereto by means of a inkjet printer an ink containing a dye of the Formula (1) or a salt thereofas defined in the first aspect of the invention or a compositionaccording to the third aspect of the present invention.

The ink jet printer preferably applies the ink to the substrate in theform of droplets which are ejected through a small orifice onto thesubstrate. Preferred ink jet printers are piezoelectric ink jet printersand thermal ink jet printers. In thermal ink jet printers, programmedpulses of heat are applied to the ink in a reservoir by means of aresistor adjacent to the orifice, thereby causing the ink to be ejectedin the form of small droplets directed towards the substrate duringrelative movement between the substrate and the orifice. Inpiezoelectric ink jet printers the oscillation of a small crystal causesejection of the ink from the orifice.

The substrate is preferably paper, plastic, a textile, metal or glass,more preferably paper, an overhead projector slide or a textilematerial, especially paper.

Preferred papers are plain or treated papers which may have an acid,alkaline or neutral character. Examples of commercially available papersinclude, HP Premium Coated Paper, HP Photopaper (all available fromHewlett Packard Inc), Stylus Pro 720 dpi Coated Paper, Epson PhotoQuality Glossy Film, Epson Photo Quality Glossy Paper (available fromSeiko Epson Corp.), Canon HR 101 High Resolution Paper, Canon GP 201Glossy Paper, Canon HG 101 High Gloss Film (all available from CanonInc.), Wiggins Conqueror paper (available from Wiggins Teape Ltd), XeroxAcid Paper and Xerox Alkaline paper, Xerox Acid Paper (available fromXerox).

A fifth aspect of the present invention provides a substrate, preferablya paper, an overhead projector slide or a textile material, printed witha composition according to the first aspect of the present invention orby means of the process according to the fourth aspect of the presentinvention.

When the substrate is a textile material the ink according to theinvention is preferably applied thereto by:

i) applying the ink to the textile material using an ink jet printer;and

ii) heating the printed textile material at a temperature of from 50° C.to 250° C.

Preferred textile materials are natural, synthetic and semi-syntheticmaterials. Examples of preferred natural textile materials include wool,silk, hair and cellulosic materials, particularly cotton, jute, hemp,flax and linen. Examples of preferred synthetic and semi-syntheticmaterials include polyamides, polyesters, polyacrylonitriles andpolyurethanes.

The textile material is preferably pre-treated with an aqueouspre-treatment composition comprising a thickening agent and optionally awater-soluble base and a hydrotropic agent and dried prior to applyingthe ink. The pre-treatment composition preferably comprises a solutionof the base and the hydrotropic agent in water containing the thickeningagent. Particularly preferred pre-treatment compositions are describedin EP 534,660A.

According to a sixth aspect of the present invention there is providedan ink jet printer cartridge comprising a chamber and ink, wherein theink is present in the chamber and the ink comprises a compositionaccording to the first aspect of the invention or a compositionaccording to the third aspect of the invention.

According to a seventh aspect of the present invention there is providedan ink jet printer containing an ink jet printer cartridge, wherein theink jet printer cartridge is as defined in the sixth aspect of thepresent invention.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise stated.

EXAMPLE 1 Dye (1)

Dye 1 was Prepared in Accordance with Following Process

Stage (a): Diazotisation and Coupling

Anthranilic acid (13.7 g, 0.1M) was dissolved in 500 ml water at pH 8(2M NaOH), screened then added sodium nitrite (8.28 g, 0.1 2M).Concentrated hydrochloric acid (30 ml) in ice and water (100 ml) at <5°C. was to this solution at <5° C. over 20 minutes. The mixture was thenstirred for 2 hours at <5° C. and excess nitrous acid was destroyedusing sulphamic acid.

Acetyl H-acid (51.8 g, 0.1M) was dissolved in 500 ml water, screenedthen allowed to stir at <5° C. while the above solution was added slowlyover 30 minutes whilst maintaining the pH 7-8 with 2M NaOH and thetemperature <5° C. The mixture was left to stir for 2 hours at <5° C.and pH 7-8, then the product was salted out using 20% w/v NaCl. Theprecipitate was filtered off and washed well with saturated brine thenpulled dry on a filter.

Stage (b): Hydrolysis

The product of stage (a) was hydrolysed in 1 litre of water and 170 mlconcentrated sodium hydroxide at 80° C. for 4 hours. The solution wasthen neutralised while hot to pH 8 using concentrated hydrochloric acid.The product was salted out by addition of 20% w/v NaCl, filtered off andwashed well with saturated brine, pulled dry on a filter and then driedin the oven at 50° C.

Stage (c): Condensation with Cyanuric Chloride

The product of stage (b) (60 g, 0.087M) was stirred in 1 litre of wateradjusted to pH 8.5 using 2M NaOH. The resulting suspension was cooled to<5° C. then cyanuric chloride (17.64 g, 0.096M dispersed in 50 ml waterwith calsolene oil) was added and the reaction mixture was left to stirat <5° C. for 2 hours maintaining pH 6.5 by the addition of 2M NaOH.

Stage (d): Condensation with Ethylenediamine

Ethylenediamine (2.87 g, 0.048M) was added to the product of stage (c)which raised the pH to 10.2. The pH was then maintained at pH 8.5 (using2 m NaOH) overnight while allowing the reaction mixture to warm to roomtemperature. The resulting product had a thick jelly like consistencyand was not isolated (2 litres).

Stage (e): Condensation with Mercaptopropionic Acid

500 ml of the product from stage (d) (0.0217M) was stirred then3-mercaptopropionic acid (13.84 g, 0.13M) was added all at once followedby a spatula end of 4-dimethylaminopyridine (catalyst). The pH wasraised to 9.7 using 2M NaOH, then the solution was heated at 90° C.whilst maintaining the pH at 9.7 using 2M NaOH for 1 hour.

The product was salted to 20% w/v with NaCl then precipitated out bylowering pH down to 5 with concentrated hydrochloric acid. Theprecipitate was filtered off then washed well with meths 740 p. Thetitle product was re-dissolved in 300 ml water using 2M NaOH, thendialysed using Viking tubing to <50ms/cm. The solution was filteredthrough 6f/f filter paper then dried in an oven at 50° C.

EXAMPLE 2 Dyes (2) to (15)

Dyes (2) to (15) of the Formula (B) were prepared by condensing thecompound of the formula HX—L—XH shown in Table 1 with approximately 2molar equivalents of the product of stage (c) in Example 1. Theresulting product was then condensed with the compound of the formula ZHshown in Table 1. The condensations were performed under analogousconditions to those used in stages (d) and (e) of Example 1

TABLE 1 Dye HX—L—XH ZH Dye (2)  NH₂(CH₂)₃NH₂ HO(CH₂)₂O(CH₂)₂NH₂ Dye (3) NH₂(CH₂)₃NH₂ HO(CH₂)₂NH₂ Dye (4)  NH₂(CH₂)₂NH₂ HO(CH₂)₂NH₂ Dye (5) NH₂(CH₂)₂NH₂ HO(CH₂)₂O(CH₂)₂NH₂ Dye (6)  NH₂(CH₂)₂NH₂ HN(CH₂CH₂OH)₂ Dye(7)  NH₂(CH₂)₃NH₂ HN(CH₂CH₂OH)₂ Dye (8)  NH₂(CH₂)₃NH₂ HS(CH₂)₂COOH Dye(9)  1,4-diaminocyclohexane HN(CH₂)₂O(CH₂)₂OH Dye (10)1,4-diaminocyclohexane HS(CH₂)₂COOH Dye (11) NH₂(CH₂)₂NH₂ H₂S Dye (12)NH₂(CH₂)₂NH₂ HN(CH₃)(CH₂)₂SO₃H Dye (13) NH₂(CH₂)₂NH₂ HNCH₂CH(OH)CH₂OHDye (14) NH₂(CH₂)₂SH NH₃ Dye (15) NH₂(CH₂)₂SH HN(CH₂)₂CH(OH)CH₂OH

EXAMPLE 3 Dyes (16) and (26) of the Formula (C):

Dyes (16) and (26) were prepared by condensing the compound of theformula HXL—XH shown in Table 2 with approximately 2 molar equivalentsof the product of stage (c) in Example 1. The resulting product was thenhydrolysed by heating in aqueous sodium hydroxide to give the titleproduct.

TABLE 2 Dye HX—L—XH Dye (16) NH₂(CH₂)₂NH₂ Dye (17) NH₂(CH₂)₃NH₂ Dye (18)1,4-diaminocyclohexane Dye (19) NH₂(CH₂)₅NH₂ Dye (20) SH(CH₂)₂SH Dye(21) SH(CH₂)₂O(CH₂)₂O(CH₂)₂SH Dye (22) NH₂CH₂CH(OH)CH₂NH₂ Dye (23)NH₂(CH₂)₂S₂(CH₂)₂NH₂ Dye (24) NH₂(CH₂)₇NH₂ Dye (25) NH₂(CH₂)₉NH₂

EXAMPLE 4 Dye (26)

Dye (26) was prepared using an analogous method to that described inExample 1, except that the anthranilic acid used in stage (a) wasreplaced with -2-amino,5-methylbenzoic acid; in place of theethylenediamine used in stage (d) was used 1,3-diamino-2-hydroxypropane;and the product of stage (d) was hydrolysed by heating in aqueous sodiumhydroxide to give the title product.

EXAMPLE 5 Inks and Ink Jet Printing

The dyes described in Examples 1 to 4 may be formulated into inks bydissolving the dye(s) in a suitable ink medium and filtering thesolution through a 0.45 μm filter. For example a suitable ink consistsof 3.5 parts dye in 96.5 parts of a medium consisting of:

5 parts 2-pyrrolidone;

5 parts thiodiglycol;

2 parts Surfynol 465 (a non-ionic surfactant available from Air ProductsInc.); and

88 parts water.

When ink jet printed onto paper, the inks provide prints which are abright magenta shade with a high water-fastness, good light fastness anda high optical density.

EXAMPLE 6

The inks described in Tables 3, 4 and 5 may be prepared wherein the Dyedescribed in the first column is the Dye made in the above Examples 1 to4. Numbers quoted in the second column onwards refer to the number ofparts of the relevant ingredient and all parts are by weight. The inksmay be applied to paper by thermal or piezo ink jet printing.

The following abbreviations are used in Tables 3, 4, and 5:

PG = propylene glycol NMP = N-methyl pyrrolidone CYC = cyclohexanol P12= propane-1,2-diol CET = cetyl ammonium bromide TBT = tertiary butanolGLY = glycerol PEG 200 = Polyethylene glycol   (average molecular weightof 200) H-1,6 = Hexane 1,6-diol CAP-L = caprolactam DEG-MBE = diethyleneglycol monobutyl ether EG = ethylene glycol DEG = diethylene glycol TFP= 2,2,3,3-tetrafluoropropanol 2P = 2-pyrrolidone UR = Urea PHO = Na₂HPO₄and TDG = thiodiglycol P-1,5 = Pentane-1,5-diol CAP = caprolactone TEA =triethanolamine BUT = γ-butyrolactone

TABLE 3 Ink Dye Dye Content Water PG DEG NMP P-1,5 TEA CYC BUT CAP EGCAP-L 1 1 3.0 90 5 4.8 0.2 2 2 10.0 85 3 3 3 5 3 2 2.1 91 8 1 1 4 3 3.186 5 0.2 4 4.8 5 4 1.1 81 9 0.5 0.5 6 5 2.5 60 4 15 3 3 6 9 4 7 6 5 6520 5 10 5 8 6 2.4 75 5 4 5 6 5 9 10 4.1 80 3 5 2 9.7 0.3 10 7 3.2 65 5 46 5 4 5 11 8 5.1 96 4 6 12 9 10.8 90 5 5 13 10 10.0 80 2 6 2 5 1 14 91.8 80 5 4 15 6 2.6 84 11 15 16 5 3.3 80 2 10 2 5 6 17 5 12.0 90 7 0.32.7 18 6 5.4 69 2 20 2 1 3 3

TABLE 4 Ink Dye Dye Content Water GLY DEG NMP CET TBT TDG UR PHO 2P Pl219 1 3.0 80 15 0.2 4.8 20 2 9.0 90 5 1.2 5 21 3 1.5 85 3.8 5 0.16 4.640.2 22 4 2.5 90 6 3.88 0.12 23 5 3.1 82 4 8 0.3 5.7 24 6 0.9 85 10 4.80.2 25 7 8.0 90 4.7 5 0.3 26 8 4.0 70 10 4 1 4 11 27 9 2.2 75 4 10 3 2 628 10 10.0 91 6 3 29 7 9.0 76 9 7 2.05 0.95 5 30 8 5.0 78 5 11 6 31 65.4 86 7 7 32 8 2.1 70 5 5 5 0.1 0.2  0.1 5 0.1 9.5 33 3 2.0 90 10 34 22 88 2 10 35 4 5 78 5 12 5 36 2 8 70 2 8 15 5 37 1 10 80 8 12 38 9 10 8010

TABLE 5 Ink Dye Dye Content Water PEG-200 DEG-MBE NMP H-1,6 TEA TFP BUTCAP EG CAP-L 39 1 2.0 80 5 6 4 5 40 2 3.0 90 5 4.8 0.2 41 3 10.0 85 3 33 5 1 42 4 2.1 91 8 1 43 6 3.1 86 5 0.2 3.8 5 44 8 1.1 81 9 0.5 0.5 9 459 2.5 60 4 15 3 3 6 5 4 46 10 5 65 20 10 47 6 2.4 75 5 4 5 6 5 48 7 4.180 3 5 2 9.7 0.3 49 8 3.2 70 5 4 6 5 4 6 5 50 8 5.1 96 4 51 1 10.8 90 55 52 2 10.0 80 2 6 2 5 1 4 53 3 1.8 80 5 15 54 4 2.6 84 11 5 55 5 3.3 802 10 2 6 56 6 12.0 90 7 0.3 2.8 57 7 5.4 69 2 20 2 1 3 3 58 8 6.0 91 4 5

What is claimed is:
 1. A composition comprising: (a) a liquid mediumcomprising (i), (ii) or (iii): (i) a mixture of water and an organicsolvent; (ii) an organic solvent free from water; or (iii) a low meltingpoint solid; and (b) a dye of the Formula (1) or salt thereof:

 wherein: each A independently is N, C—Cl, C—CN or C—NO₂; each Bindependently is a substituent other than —COOH; L is optionallyinterrupted alkylene, optionally substituted by halo or —OH, wherein theoptional interruption(s) are selected from the group consisting of —S—,—NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—; each Z independently is —SR²,—OR³, —NR⁴R⁵ or a labile atom or group; each X independently is —S—, —O—or —NR¹—; each R¹ independently is H or optionally substituted alkyl;R², R³, R⁴ and R⁵ are each independently H, optionally substitutedalkyl, optionally substituted aryl or optionally substituted aralkyl; orR⁴ and R⁵ together with the nitrogen to which they are attached form anoptionally substituted five or six membered ring; and each nindependently is 0 to
 4. 2. A composition according to claim 1 which hasa concentration of less than 100 parts per million in total of halideions and divalent and trivalent metals ions.
 3. A composition accordingto claim 1 wherein L is C₂₋₆-alkylene.
 4. A composition according toclaim 1 wherein each B independently is —SO₃H, —PO₃H₂, —CF₃, optionallysubstituted alkoxy, optionally substituted alkyl, optionally substitutedamino, halo, —CN, —SO₂—T, —OH or —NO₂, wherein T is optionallysubstituted alkyl, optionally substituted aryl, vinyl, or a groupconvertible to vinyl on treatment with aqueous alkali.
 5. A compositionaccording to claim 1 wherein each Z independently is —SR², —OR³ or—NR⁴R⁵ wherein R², R³, R⁴ and R⁵ are each independently H, optionallysubstituted alkyl, optionally substituted aryl or optionally substitutedaralkyl; or R⁴ and R⁵ together with the nitrogen to which they areattached form an optionally substituted five or six membered ring.
 6. Acomposition according to claim 1 wherein L is C₂₋₆-alkylene optionallyinterrupted by —S—, —CH═CH— or —NR¹— wherein R¹ is H or optionallysubstituted alkyl.
 7. A composition according to claim 1 wherein the dyeof Formula (1) is of Formula (2) or a salt thereof:

wherein: L¹ is optionally interrupted C₂₋₂₀-alkylene, wherein theoptional interruption(s) are selected from the group is consisting of[—O—,] —S—, —CR⁹═CR⁹— and —NR⁹—; each R⁹ independently is H orC₁₋₄-alkyl optionally substituted by —OH, —COOH, —SO₃H or —CN; and eachZ independently is SR², —OR³, —NR⁴R⁵ or a labile atom or group whereinR², R³, R⁴ and R⁵ are each independently H, optionally substitutedalkyl, optionally substituted aryl or optionally substituted aralkyl; orR⁴ and R⁵ together with the nitrogen to which they are attached form anoptionally substituted five or six membered ring.
 8. A compositionaccording to claim 7 wherein L¹ is C₂₋₆-alkylene.
 9. A compositionaccording to claim 1 which further contains one or more magenta dye(s)other than a dye of Formula (1) or a salt thereof.
 10. A compositionaccording to claim 1 which is an ink.
 11. A dye of the Formula (1) orsalt thereof:

wherein: each A independently is N, C—Cl, C—CN or C—NO₂; each Bindependently is a substituent other than —COOH; L is optionallyinterrupted C₂₋₆-alkylene, optionally substituted by halo or —OH,wherein the optional interruption(s) are selected from the groupconsisting of —S—, —NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—; each Zindependently is —SR², —OR³ or —NR⁴R⁵; and each X independently is —S—,—O— or —NR¹—; each R¹ independently is H or optionally substitutedalkyl; R², R³, R⁴ and R⁵ are each independently H, optionallysubstituted alkyl, optionally substituted aryl or optionally substitutedaralkyl; or R⁴ and R⁵ together with the nitrogen to which they areattached form an optionally substituted five or six membered ring; andeach n independently is 0 to
 4. 12. A dye according to either claim 11wherein: each B independently is —SO₃H, —PO₃H₂, —CF₃, optionallysubstituted alkoxy, optionally substituted alkyl, optionally substitutedamino, halo, —CN, —SO₂—T, —OH or —NO₂; and T is optionally substitutedalkyl, optionally substituted aryl, vinyl, or a group convertible tovinyl on treatment with aqueous alkali.
 13. A dye of the Formula (2) orsalt thereof:

wherein: L¹ is optionally interrupted C₂₋₆-alkylene, wherein theoptional interruption(s) are selected from the group consisting of —S—,—CR⁹═CR⁹— or —NR⁹—; each R⁹ independently is H or C₁₋₄-alkyl optionallysubstituted by —OH, —COOH, —SO₃H or —CN; each Z independently is —SR²,—OR³, —NR⁴R⁵ or a labile atom or group; R², R³, R⁴ and R⁵ are eachindependently H, optionally substituted alkyl, optionally substitutedaryl or optionally substituted aralkyl; or R⁴ and R⁵ together with thenitrogen to which they are attached form an optionally substituted fiveor six membered ring.
 14. A dye according to claim 13 wherein: L¹ isC₂₋₄-alkylene; each Z independently is —NR⁷R⁸; R⁷ is C₁₋₆-alkyloptionally substituted by —OH, C₁₋₄-alkoxy, C₁₋₄-hydroxyalkoxy, —COOH or—SO₃H; and R⁸ independently is as defined for R⁷or H.
 15. A compositioncomprising: (i) from 1 to 99 parts in total of one or more dye(s) of theFormula (1) or salts thereof; and (ii) from 99 to 1 parts in total ofone or more water-soluble magenta dye(s) other than a dye of the Formula(1) or salt thereof;

 wherein: each A independently is N, C—Cl, C—CN or C—NO₂; each Bindependently is a substituent other than —COOH; L is optionallyinterrupted C₂₋₆-alkylene, optionally substituted by halo or —OH,wherein the optional interruption(s) are selected from the groupconsisting of [—O—,] —S—, —NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—; each Zindependently is —SR², —OR³, —NR⁴R⁵ or a labile atom or group; each Xindependently is —S—, —O— or —NR¹—; each R¹ independently is H oroptionally substituted alkyl; R², R³, R⁴ and R⁵ are each independentlyH, optionally substituted alkyl, optionally substituted aryl oroptionally substituted aralkyl; or R⁴ and R⁵ together with the nitrogento which they are attached form an optionally substituted five or sixmembered ring; and each n independently is 0 to 4; wherein all parts areby weight and the sum of the parts (i) and (ii)=100.
 16. A process forprinting an image on a substrate comprising applying thereto by means ofan ink jet printer (i) an ink containing a dye of Formula (1) or a saltthereof:

wherein: each A independently is N, C—Cl, C—CN or C—NO₂; each Bindependently is a substituent other than —COOH; L is optionallyinterrupted C₂₋₆-alkylene, optionally substituted by halo or —OH,wherein the optional interruption(s) are selected from the groupconsisting of —S—, —NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—; each Zindependently is —SR², —OR³, —NR⁴R⁵ or a labile atom or group; each Xindependently is —S—, —O— or —NR¹—; each R¹ independently is H oroptionally substituted alkyl; R², R³, R⁴ and R⁵ are each independentlyH, optionally substituted alkyl, optionally substituted aryl oroptionally substituted aralkyl; or R⁴ and R⁵ together with the nitrogento which they are attached form an optionally substituted five or sixmembered ring; and each n independently is 0 to 4, or (ii) a compositionaccording to claim 15, by means of an ink jet printer.
 17. A substrateprinted with a composition according to claim
 1. 18. An ink jet printercartridge comprising a chamber and ink, wherein the ink is present inthe chamber and the ink comprises a composition according to claim 1.19. An ink jet printer containing an ink jet printer cartridge, whereinthe ink jet printer cartridge is as defined in claim
 18. 20. A substrateprinted by a process comprising applying thereto by means of an ink jetprinter an ink containing a dye of Formula (1) or a salt thereof:

wherein: each A independently is N, C—Cl, C—CN or C—NO₂; each Bindependently is a substituent other than —COOH; L is optionallyinterrupted C₂₋₆-alkylene, optionally substituted by halo or —OH,wherein the optional interruption(s) are selected from the groupconsisting of —S—, —NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—; each Zindependently is —SR², —OR³, —NR⁴R⁵ or a labile atom or group; each Xindependently is —S—, —O— or —NR¹—; each R¹ independently is H oroptionally substituted alkyl; R², R³, R⁴ and R⁵ are each independentlyH, optionally substituted alkyl, optionally substituted aryl oroptionally substituted aralkyl; or R⁴ and R⁵ together with the nitrogento which they are attached form an optionally substituted five or sixmembered ring; and each n independently is 0 to
 4. 21. A substrateaccording to claim 20, wherein said ink comprises a compositioncomprising: (i) from 1 to 99 parts in total of one or more dye(s) of theFormula (1) or salts thereof as defined above; and (ii) from 99 to 1parts in total of one or more water-soluble magenta dye(s) other than adye of the Formula (1) or salt thereof as defined above; wherein allparts are by weight and the sum of the parts (i) and (ii)=100 by meansof an ink jet printer.
 22. An ink jet printer cartridge comprising achamber and ink, wherein the ink is present in the chamber and the inkcomprises a composition according to claim
 15. 23. An ink jet printercontaining an ink jet printer cartridge, wherein the ink jet printercartridge is as defined in claim
 22. 24. A composition comprising: (a) aliquid medium comprising (i), (ii) or (iii): (i) a mixture of water andan organic solvent; (ii) an organic solvent free from water; or (iii) alow melting point solid; and (b) a dye of the Formula (1) or a saltthereof:

 wherein: each A independently is N, C—Cl, C—CN or C—NO₂; each Bindependently is a substituent other than —COOH; L is optionallyinterrupted alkylene, optionally substituted by halo or —OH, wherein theoptional interruption(s) are selected from the group consisting of —O—,—S—, —NR¹—, —CR¹═CR¹—, —C(O)— and —C(O)O—; each Z independently is —SR²,—OR³, —NR⁴R⁵ or a labile atom or group; each X independently is —S—, —O—or —NR¹—; each R¹ independently is optionally substituted alkyl; R², R³,R⁴ and R⁵ are each independently H, optionally substituted alkyl,optionally substituted aryl or optionally substituted aralkyl; or R⁴ andR⁵ together with the nitrogen to which they are attached form anoptionally substituted five or six membered ring; and each nindependently is 0 to
 4. 25. A composition comprising: (a) a liquidmedium comprising (i), (ii) or (iii): (i) a mixture of water and anorganic solvent; (ii) an organic solvent free from water; or (iii) a lowmelting point solid; and (b) a dye of the Formula (1) or a salt thereof:

 wherein: each A independently is N, C—Cl, C—CN or C—NO₂; each Bindependently is a substituent other than —COOH; L is alkylene,optionally substituted by halo or —OH; each Z independently is —SR²,—OR³, —NR⁴R⁵ or a labile atom or group; each X independently is —S—, —O—or —NR¹—; each R¹ independently is H or optionally substituted alkyl;R², R³, R⁴ and R⁵ are each independently H, optionally substitutedalkyl, optionally substituted aryl or optionally substituted aralkyl; orR⁴ and R⁵ together with the nitrogen to which they are attached form anoptionally substituted five or six membered ring; and each nindependently is 0 to
 4. 26. A composition according to claim 25,wherein in L, the alkylene has from 2 to 6 carbon atoms.
 27. Acomposition according to claim 24 wherein the dye of Formula (1) is ofFormula (2) or a salt thereof:

wherein: L¹ is optionally interrupted C₂₋₂₀-alkylene, wherein theoptional interruption(s) are selected from the group is consisting of—O—, —S—, —CR⁹═CR⁹— and —NR⁹—; each R⁹ independently is C₁₋₄-alkyloptionally substituted by —OH, —COOH, —SO₃H or —CN; and each Zindependently is SR², —OR³, —NR⁴R⁵ or a labile atom or group wherein R²,R³, R⁴ and R⁵ are each independently H, optionally substituted alkyl,optionally substituted aryl or optionally substituted aralkyl; or R⁴ andR⁵ together with the nitrogen to which they are attached form anoptionally substituted five or six membered ring.